EP1059278B1 - Verfahren zur Herstellung von Epichlorohydrin und Zwischenprodukt davon - Google Patents

Verfahren zur Herstellung von Epichlorohydrin und Zwischenprodukt davon Download PDF

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Publication number
EP1059278B1
EP1059278B1 EP00112079A EP00112079A EP1059278B1 EP 1059278 B1 EP1059278 B1 EP 1059278B1 EP 00112079 A EP00112079 A EP 00112079A EP 00112079 A EP00112079 A EP 00112079A EP 1059278 B1 EP1059278 B1 EP 1059278B1
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Prior art keywords
compound
catalyst
reaction
except
same manner
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EP1059278A2 (de
EP1059278A3 (de
Inventor
Takanori c/oKawasaki Plant Showa Denko K.K. Aoki
Takami c/o Kawasaki Plant Showa Denko K.K. Ohe
Haruki c/oKawasaki Plant Showa Denko KK Ishikami
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Resonac Holdings Corp
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Showa Denko KK
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Priority claimed from JP2000131145A external-priority patent/JP4385487B2/ja
Priority claimed from JP2000131146A external-priority patent/JP4548556B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
    • C07D301/26—Y being hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to a process for the production of epichlorohydrin and dichloropropanol which is an intermediate of epichlorohydrin.
  • Epichlorohydrin is useful as a raw material for the production of various compounds or as a solvent, a raw material for epoxy resins, a raw material for synthetic rubbers, a stabilizer for chlorinated rubbers and the like.
  • Epichlorohydrin is produced through a step of reacting allyl alcohol with chlorine to produce dichloropropanol and a step for dehydrochlorinating dichloropropanol to produce epichlorohydrin.
  • dichloropropanol refers to 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol or a mixture thereof.
  • An object of the present invention is to solve the problems in conventional production methods for dichloropropanol, i.e., in the liquid phase chlorination methods, in a process for producing epichlorohydrin. More specifically, it is to solve problems attributable to the use of hydrochloric acid or hydrogen chloride, such as need of a step for recovering hydrochloric acid or hydrogen chloride, recovery loss thereof, and energy loss accompanying the external cooling, so that dichloropropanol can be produced industrially advantageously, whereby a process for producing epichlorohydrin more industrially advantageous can be provided.
  • the present inventors have found that the object of the present invention can be attained by a process, for producing dichloropropanol, comprising reacting allyl alcohol with chlorine in a gaseous phase.
  • the present invention has been accomplished based on this finding.
  • the present invention provides a process for producing dichloropropanol comprising reacting allyl alcohol with chlorine in a gaseous phase.
  • the present invention provides a process for producing epichlorohydrin comprising:
  • the allyl alcohol for use in the present invention may be any commercially or industrially available allyl alcohol and is not particularly limited.
  • the chlorine for use in the present invention may be any commercially or industrially available chlorine and is not particularly limited.
  • the reaction of allyl alcohol with chlorine in a gaseous phase may preferably be effected in the presence of a catalyst.
  • the catalyst for use in the production of dichloropropanol according to the present invention may suitably be a catalyst containing at least one element selected from the elements of Groups 1 to 16 of the long-form Periodic Table or at least one compound containing the at least one element.
  • Examples of the element include Li, Na, K, Rb and Cs of Group 1 of the long-form Periodic Table, Be, Mg, Ca, Sr and Ba of Group 2, Y, Sc, lanthanoid element and actinoid element of Group 3, Ti, Zr and Hf of Group 4, V, Nb and Ta of Group 5, Cr, Mo and W of Group 6, Mn, Tc and Re of Group 7, Fe, Ru and Os of Group 8, Co, Rh and Ir of Group 9, Ni, Pd and Pt of Group 10, Cu, Ag and Au of Group 11, Zn and Cd of Group 12, Al, Ga, In and Tl of Group 13, Si, Ge, Sn and Pb of Group 14, P, As, Sb and Bi of Group 15, and Se and Te of Group 16.
  • the element is by no means limited thereto. Of these elements, the elements of Groups 1, 2, 3, 7, 9, 12, 15 and 16 of the long-form Periodic Table are preferred.
  • the compound of the element include halides, oxides, carbonates, phosphates, nitrates, sulfates, oxyhalides, basic carbonates, hydroxides, carboxylates and organic metal complexes of the above-described elements.
  • the compound of the element is not limited thereto. Among these compounds, halides and oxides are preferred.
  • halogen of the halides or oxyhalides examples include fluorine, chlorine, bromine and iodine, Of these, chlorine and fluorine are preferred.
  • the catalyst for use in the present invention may be used in any known form such as liquid or solid and the form is not particularly limited.
  • the catalyst is preferably a catalyst of a supported type, a coprecipitated type, an ion exchanged type, a precipitated type, a kneaded type, a melted type, a hydrothermally synthesized type or a gas phase-synthesized type, more preferably a supported type catalyst in which at least one element selected from the elements of Groups 1 to 16 of the long-form Periodic Table or at least one compound containing the at least one element is supported on a support.
  • the element or compound per se may of course be used as a catalyst as it is.
  • Activated carbon is an example of the use of an element as a catalyst as it is.
  • the at least one element selected from Groups 1 to 16 of the long-form Periodic Table or the compound of the element may suitably be contained in the catalyst in a concentration of from 0.01 to 100 wt%, preferably from 0.1 to 100 wt%, based on the total weight of the catalyst.
  • concentration is not limited thereto.
  • the support is not particularly limited, and specific examples thereof include single oxides such as alumina, zirconia, titania, niobia, silica and magnesia, composite oxides such as silica-alumina, silica-magnesia and silica-calcia, stratum compounds, zeolite, heteropoly acids, activated carbon, silicon carbide, silicon nitride and polymers.
  • the support may contain the same element as the at least one element selected from the element of Groups 1 to 16 of the long-form Periodic Table to be employed in the catalyst.
  • the catalyst for use in the present invention can be prepared as described below.
  • a compound is dissolved or suspended in an appropriate solvent such as water, alcohol, hydrochloric acid or aqueous ammonia, in an amount such that the support can absorb the solution or suspension.
  • a support having an appropriate particle size is added to the solution or suspension to be impregnated therewith and then dried.
  • the drying may be performed either under atmospheric pressure or a reduced pressure.
  • the support in the case of drying the catalyst under atmospheric pressure, the support can be dried at from 20 to 300°C in an air dryer or the like.
  • the support can be dried at from 20 to 300°C in a vacuum dryer or the like. The drying is preferably continued until the catalyst reaches a constant weight.
  • the dried supported catalyst can be used as it is in the reaction or may be used after being calcined.
  • the calcination may be performed in an atmosphere of nitrogen, carbon dioxide gas, air, oxygen, hydrogen or the like, but the atmosphere is not particularly limited as far as it is matches the purpose.
  • the calcination may be performed in an atmosphere inactive to the compound of at least one element selected from elements of Groups 1 to 16 of the long-form Periodic Table.
  • the calcination is preferably performed in a nitrogen atmosphere.
  • a catalyst containing an oxide of at least one element selected from elements of Groups 1 to 16 of the long-form Periodic Table any known method may be used.
  • a catalyst containing a compound of at least one element selected from elements of Groups 1 to 16 of the long-form Periodic Table may be oxidized by calcination in an atmosphere containing an oxidizing agent such as oxygen or air.
  • an oxidizing agent such as oxygen or air.
  • the preparation method is not limited thereto.
  • any known preparation method may be used.
  • a catalyst containing a compound of at least one element selected from elements of Groups 1 to 16 of the long-form Periodic Table may be reduced by calcination in an atmosphere containing a reducing agent such as hydrogen, paraffin or an olefin.
  • a reducing agent such as hydrogen, paraffin or an olefin.
  • the preparation method is not limited thereto.
  • the calcination temperature is not particularly limited but may preferably be higher than the reaction temperature. Also, the calcination time is not particularly limited but the calcination may preferably be performed until the catalyst reaches a constant weight.
  • any known method may be used.
  • the two or more elements or compounds of the elements may be supported in any order.
  • the two or more elements or compounds of the elements may be supported separately or simultaneously. These are not particularly limited.
  • the shape of the solid catalyst for use in the present invention is not particularly limited and any shape may be used, such as of a tablet, a ring, a sphere, a micro-ball or an extruded article.
  • the shaping may be performed by any known method such as compression molding, extrusion molding and spray dry granulation.
  • the catalyst may be used after being blended with an inactive filler.
  • the filler for use in the present invention is not particularly limited as long as it is a solid substance, and examples thereof include glass beads, silicon carbide and silicon nitride, however, the present invention is not limited thereto.
  • the catalyst and the filler may be blended by any known method such as a method of uniformly blended or a method of varying the blending ratio of the catalyst and the filler in the flowing direction of the reaction gas mixture.
  • the blending method is by no means limited thereto.
  • the shape of the filler is not particularly limited and any shape such as a tablet, a ring, a sphere, a micro-ball or an extruded article may be used. Furthermore, the shape may be the same as or different from that of the catalyst.
  • water may be added at the time of reaction of allyl alcohol with chlorine in a gaseous phase.
  • the water for use in the present invention may be any if it is commercially or industrially available.
  • the water is preferably ion exchanged water, distilled water or the like, however, the present invention is not limited thereto.
  • the water may be previously mixed with allyl alcohol before being added.
  • the addition of water is effective in improving the yield of dichloropropanol.
  • conditions are preferably selected so that dichloropropanol (2,3-dichloro-1-propanol (boiling point: 182°C/101 kPa), 1,3-dichloro-2-propanol (boiling point: 174°C/101 kPa)) can be produced in a gas state.
  • dichloropropanol 2,3-dichloro-1-propanol (boiling point: 182°C/101 kPa), 1,3-dichloro-2-propanol (boiling point: 174°C/101 kPa)
  • it is more preferred to add a diluent.
  • the diluent for use in the present invention is not particularly limited as long as it does not inhibit the production of dichloropropanol.
  • the diluent is preferably an inert gas.
  • the inert gas is not particularly limited and, for example, nitrogen, carbon dioxide, helium, argon or the like may be used. However, the present invention is not limited thereto. Among these, nitrogen is preferred.
  • composition of raw material gas for use in the production of dichloropropanol may preferably be freely selected from the range that allyl alcohol is from 0.01 to 99.99 mol%, chlorine is from 0.00001 to 60 mol%, water is from 0 to 99.99 mol% and the diluent is from 0 to 99.99 mol%.
  • the composition of the raw material gas is preferably selected so that dichloropropanol produced can be maintained in the gas state.
  • the raw material gas composition is preferably selected so that the partial pressure of dichloropropanol produced can be lower than the saturated vapor pressure of dichloropropanol at the reaction temperature.
  • the molar ratio of chlorine to allyl alcohol (chlorine/allyl alcohol) used in the present invention may suitably be from 0.001 to 1.5, preferably from 0.01 to 1.2. If the molar ratio of chlorine/allyl alcohol exceeds 1.5, this may cause problems, for example, a side reaction such as displacement reaction may take place due to excess chlorine or a large amount of unreacted chlorine must be recovered. On the other hand, if the molar ratio of chlorine/allyl alcohol is less than 0.001, a large amount of allyl alcohol may have to be disadvantageously recovered.
  • the molar ratio of water to allyl alcohol (water/allyl alcohol) used in the present invention may suitably be from 0 to 1,000, preferably from 0.0001 to 100, however, the molar ratio is by no means limited thereto.
  • the molar ratio of diluent to chlorine (diluent/ chlorine) used in the present invention may suitably be from 0 to 2,000, preferably from 0 to 1,000, however, the molar ratio is by no means limited thereto.
  • the raw material gas for use in the production of dichloropropanol of the present invention may suitably flow at a space velocity of from 100 to 120,000 hr -1 , preferably from 300 to 40,000 hr -1 , however, the present invention is not limited thereto.
  • the reaction temperature in the production of dichloropropanol may suitably be from 70 to 300°C, preferably from 80 to 250°C. If the reaction temperature exceeds 300°C, reduction of catalyst life or the like may disadvantageously result due to an increase of a displacement reaction product with chlorine or side production or accumulation of high boiling point compounds. On the other hand, if the reaction temperature is less than 70°C, the amount of diluent used may be increased so as to maintain the gas phase state, as a result, there may cause problems, for example, a large amount of diluent must be recycled, the productivity decreases, or the reaction encounters difficulties in proceeding in a stable gaseous phase.
  • the heat generated accompanying the reaction of allyl alcohol with chlorine may be eliminated to outside the system using water, warm water or a heating medium, so as to maintain the reaction temperature in a constant range.
  • the heat taken out by water, warm water or a heating medium may be used as a heat source for other facilities and this is beneficial.
  • the pressure in the production of dichloropropanol may suitably be from 10 to 1,000 kPa, preferably from 50 to 500 kPa. If the reaction pressure is less than 10 kPa or exceeds 1,000 kPa, practice of the process in an industrial scale may be difficult, thus, a reaction pressure outside the above-described range is not preferred.
  • reaction system for the gas phase reaction of allyl alcohol with chlorine is not particularly limited and any known reaction system may be used.
  • a continuous flow system may be suitably and preferably used.
  • the form of the reactor for use in the present invention is not particularly limited but a fixed bed reactor, a fluid bed reaction vessel and the like may be suitably and preferably used.
  • the raw material gas may be introduced into the reactor by any known method and the introduction method is not particularly limited.
  • allyl alcohol may be introduced by being previously vaporized in a vaporizer.
  • Water may be introduced by being previously vaporized in a vaporizer or may be introduced as a hydrous allyl alcohol after being mixed with allyl alcohol.
  • Chlorine may be introduced together with the previously vaporized allyl alcohol into the reactor or may be introduced separately.
  • chlorine may be introduced so that allyl alcohol and chlorine are efficiently brought into contact on a catalyst, as in a method where allyl alcohol and chlorine are previously mixed in a static mixer (see, Kagaku Sochi Chemical Apparatuses), pp.74-78 (May 1994)) and then introduced into a reactor.
  • a static mixer see, Kagaku Sochi Chemical Apparatuses
  • pp.74-78 May 1994
  • the present invention is by no means limited thereto.
  • the diluent for use in the present invention may be added to the allyl alcohol, may be added only to the chlorine or may be-added to both the allyl alcohol and the chlorine.
  • the addition system is not particularly limited and any known method may be used.
  • any known method may be used.
  • a gas component and a liquid component containing dichloropropanol produced may be separated by cooling the reactor outlet.
  • This liquid component containing dichloropropanol may be subjected to distillation and purification, whereby dichloropropanol may be obtained.
  • the inert gas after the separation of dichloropropanol may be recycled or may be purified and then reused.
  • the liquid component may contain unreacted allyl alcohol depending on the cooling temperature, but this unreacted allyl alcohol may be reused after separating it from dichloropropanol by distillation or the like. It is also possible to condense only dichloropropanol as the desired product by setting the cooling temperature to a high degree and recycling the unreacted allyl alcohol in the gas state as it is or reusing it after purification.
  • the dichloropropanol produced in the present invention includes 2,3-dichloro-1-propanol and 1,3-dichloro-2-propanol.
  • the dichloropropanol produced has a composition ratio in mol% such that 2,3-dichloro-1-propanol is from 5 to 100 mol% and 1,3-dichloro-1-propanol is from 0 to 95%.
  • These two isomers may be separated by a known method, for example, by rectification or the like. However, the separation method is not limited thereto.
  • dichloropropanol obtained as mentioned above may be used as a starting material without separating those two isomers.
  • epichlorohydrin may be performed by any known method.
  • a method of reacting dichloropropanol with an aqueous alkali solution or suspension and thereby producing epichlorohydrin may be preferably used.
  • the method is not limited thereto.
  • the alkaline compound for use in the second step is not particularly limited.
  • an aqueous solution or suspension of calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like may be used, however, the present invention is not limited thereto.
  • the amount of the alkaline compound used is not particularly limited.
  • the amount of the alkaline compound used is preferably from 1.0 to 1.5 equivalent, more preferably from 1.03 to 1.3 equivalent, per mol of dichloropropanol.
  • the reaction in the second step may also be performed by any known method.
  • Preferred examples of the method include:
  • the reaction may be performed either batchwise or continuously.
  • a mixing tank-type reaction or a flow-type reaction in a tower reactor or the like may be used.
  • a flow-type reaction in a tower reactor dichloropropanol or a solution thereof and an aqueous alkali solution or suspension may flow cocurrently or countercurrently while coming into contact, to thereby effect reaction.
  • the reaction methods (2) and (3) may be combined, for example, so that the reaction is performed by one method to a certain degree and the reaction is further allowed to proceed according to the other method.
  • the amount of steam used for the stripping of epichlorohydrin produced in the second step may suitable be such that the top distillate composition has a water/epichlorohydrin ratio by weight of from 0.5 to 3.5, preferably from 1.0 to 2.5.
  • the selectivity of epichlorohydrin increases.
  • the steam amount is too large, the steam yield may decrease so that the amount used is limited in practice, whereas if the steam amount is too small, the stripping effect may be reduced and the selectivity of epichlorohydrin may decrease.
  • the reaction temperature in the second step is not particularly limited but it is preferably from 40 to 110°C, more preferably from 60 to 100°C. As the reaction temperature becomes lower, the selectivity of epichlorohydrin increases, however, the reaction rate may decrease and the reaction time may be prolonged.
  • the reaction pressure in the second step is not particularly limited but it is preferably from 10 to 200 kPa.
  • the catalyst obtained had a composition of a compound (5 wt%)/support (95 wt%).
  • the catalyst obtained had a composition of a compound (5 wt%)/support (95 wt%).
  • a compound in an amount corresponding to 2.25 g of an oxide was dissolved or suspended in 18 g of water, and 42.75 g of a support was added thereto, impregnated with the solution or suspension at room temperature for 30 minutes, evaporated to dryness on a water bath and then air dried at 120°C for 12 hours. The dried product was calcined at 500°C for 3 hours in an air stream.
  • the catalyst obtained had an composition of an oxide (5 wt%)/support (95 wt%).
  • a catalyst was prepared using LiCl as the compound and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 1.
  • 16 ml of the catalyst was filled in a vertical glass-made reactor having an internal diameter of 14 mm and a length of 15 cm equipped with a glass tube for the measurement of temperature.
  • the reactor was heated to 140°C by a heating medium and into the reactor, a raw material gas comprising 1.3 mol% of chlorine, 3.3 mol% of allyl alcohol, 4.6 mol% of water and 90.8 mol% of nitrogen was introduced under atmospheric pressure and at a space velocity of 4,131 h -1 , and reacted.
  • the allyl alcohol and water were each previously vaporized through a vaporizer set at 140°C.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that the compound was WCl 6 and the catalyst was prepared according to Catalyst Preparation Process 2. The results are shown in Table 2.
  • Example 4 A reaction was performed in the same manner as in Example 1 except that the catalyst was ZrO 2 (particle size: 0.5 to 2.0 mm). The results are shown in Table 4.
  • Example 4 A reaction was performed in the same manner as in Example 1 except that the catalyst was TiO 2 (particle size: 0.5 to 2.0 mm). The results are shown in Table 4.
  • Example 31 A reaction was performed in the same manner as in Example 31 except that the reactor was heated to 110°C by a heating medium and the vaporizer was set at 110°C. The results are shown in Table 4.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as the compound and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 2 was filled in a reactor and a raw material gas comprising 1.3 mol% of chlorine, 3.3 mol% of allyl alcohol and 95.4 mol% of nitrogen was introduced into the reactor at a space velocity of 4,131 h -1 . The results are shown in Table 4.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as the compound and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 2 was filled in a reactor and a raw material gas comprising 1.3 mol% of chlorine and 98.7 mol% of allyl alcohol was introduced into the reactor at a space velocity of 4,131 h -1 .
  • the results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was LiCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was NaCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was KCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was RbCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CsCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was BeCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CaCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 4.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was SrCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was BaCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was YCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was ScCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was LaCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was TiCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was VCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CrCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was WCl 6 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MnCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was ReCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was FeCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was FeCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was RuCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CoCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 5.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was RhCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was NiCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was PdCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 7. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was H 2 PtCl 4 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CuCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 7. The results are shown in Table 6.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was CuCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 6.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was AgCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 7. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was InCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was SnCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was PbCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was Sb 2 O 5 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was BiCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was MgCl 2 , Compound B was CaCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was InCl 3 , Compound B was BaCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 6 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was ZrO 2 (particle size: 0.5 to 2.0 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 6.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was TiO 2 (particle size: 0.5 to 2.0 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 7.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was SiO 2 (particle size: 0.5 to 2.0 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 7.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was SiC (particle size: 1.0 to 2.0 mm) and the catalyst was prepared according to Catalyst Preparation Process 5. The results are shown in Table 7.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as Compound A, MgCl 2 as Compound B and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 5 was filled in a reactor and a raw material gas comprising 1.3 mol% of chlorine, 3.3 mol% of allyl alcohol and 95.4 mol% of nitrogen was introduced into the reactor at a space velocity of 4,131 h -1 . The results are shown in Table 7.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as Compound A, MgCl 2 as Compound B and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 5 was filled in a reactor and a raw material gas comprising 4.8 mol% of chlorine, 5.3 mol% of allyl alcohol, 7.4 mol% of water and 82.5 mol% of nitrogen was introduced into the reactor at a space velocity of 1,137 h -1 . The results are shown in Table 7.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as Compound A, MgCl 2 as Compound B and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 5 was filled in a reactor and a raw material gas comprising 4.8 mol% of chlorine, 5.3 mol% of allyl alcohol, 48.0 mol% of water and 41.9 mol% of nitrogen was introduced into the reactor at a space velocity of 1,137 h -1 . The results are shown in Table 7.
  • a reaction was performed in the same manner as in Example 1 except that a catalyst prepared using ZnCl 2 as Compound A, MgCl 2 as Compound B and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 5 was filled in a reactor and a raw material gas comprising 4.8 mol% of chlorine, 5.3 mol% of allyl alcohol and 89.9 mol% of water was introduced into the reactor at a space velocity of 1,137 h -1 . The results are shown in Table 7.
  • a reaction was performed in the same manner as in Example 1 except that 5.3 ml of a catalyst prepared using ZnCl 2 as Compound A, MgCl 2 as Compound B and Al 2 O 3 (particle size: 1.6 mm) as the support according to Catalyst Preparation Process 5 and 10.7 ml of glass beads (particle size: 0.99 to 1.4 mm) as a filler were mixed to form a homogeneous mixture as much as possible and filled in a reactor and a raw material gas comprising 4.8 mol% of chlorine, 5.3 mol% of allyl alcohol, 7.4 mol% of water and 82.5 mol% of nitrogen was introduced into the reactor based on the catalyst and filler (total: 16 ml) at a space velocity of 1,137 h -1 .
  • the results are shown in Table 7.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was TeCl 4 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 6. The results are shown in Table 7.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 8. The results are shown in Table 7.
  • Example 7 A reaction was performed in the same manner as in Example 1 except that the catalyst was activated carbon (particle size: 0.5 to 2.0 mm). The results are shown in Table 7.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was NaCl, the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 9. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was CaCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 9. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was SrCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 9. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was YCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 9. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was MnCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 10. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was CoCl 2 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 10. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was BiCl 3 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 10. The results are shown in Table 8.
  • Example 2 A reaction was performed in the same manner as in Example 1 except that Compound A was ZnCl 2 , Compound B was MgCl 2 , Compound C was TeCl 4 , the support was Al 2 O 3 (particle size: 1.6 mm) and the catalyst was prepared according to Catalyst Preparation Process 10. The results are shown in Table 8.
  • the following dehydrochlorination column was used for performing dehydrochlorination reaction of dichloropropanol and for stripping to immediately separate epichlorohydrin produced from the reaction liquid.
  • the dehydrochlorinating column body was made of glass and had an inner diameter of 55 mm ⁇ and a height of 1,500 mm.
  • 10 porous plates each having thereon 280 holes of 1 mm diameter were disposed at an interval of 100 mm and each porous plate had a downcomer of a depth of 5 mm.
  • a steam blowing nozzle was disposed to feed a constant amount of steam through a flowmeter.
  • a liquid feed nozzle was disposed to feed dichloropropanol and an aqueous alkali solution.
  • the dichloropropanol solution and the aqueous alkali solution were delivered by a metering pump and mixed immediately before the liquid feed nozzle. From the column top, the distillate is recovered through a condenser. At the column bottom, a 500 ml round bottom flask was fixed and the bottom liquid was extracted in a constant amount by a metering pump to keep the bottom amount of 40 ml.
  • the dichloropropanol obtained in Example 59 and an aqueous solution of 9.5 wt% Ca(OH) 2 slurry were fed through the liquid feed nozzle at a rate of 83 g/h and 323 g/h, respectively.
  • steam was blown through the steam blowing nozzle.
  • the concentration of dichloropropanol during the feeding was 20 wt%.
  • the operation was continued for about 2 hours until the reaction system was stabilized. After 1 hour, the top distillate and the bottom solution were sampled and the compositions were analyzed.
  • the conversion of dichloropropanol was 89.1% and the selectivity of epichlorohydrin was 97.0%.
  • the temperature in the middle column was 100°C.
  • Example 113 A reaction was performed in the same manner as in Example 113 except that the dichloropropanol obtained in Example 99 was used. As a result, the conversion of dichloropropanol was 90.2% and the selectivity of epichlorohydrin was 96.8%. The temperature in the middle column was 99°C.
  • dichloropropanol can be obtained in a high yield and at a high selectivity. Also, dichloropropanol can be produced without the problems encountered in a conventional liquid phase reaction, such as need of a step for the separation and recovery of hydrochloric acid, loss of hydrochloric acid in the recovery step and energy loss accompanying the cooling.
  • epichlorohydrin can be efficiently manufactured from dichloropropanol obtained by reacting allyl alcohol with chlorine in a gaseous phase.

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  • Epoxy Compounds (AREA)

Claims (13)

  1. Verfahren zur Herstellung von Dichlorpropanol, welches das Umsetzen von Allylalkohol mit Chlor in einer Gasphase umfaßt.
  2. Verfahren nach Anspruch 1, wobei die Reaktion in Anwesenheit eines Katalysators durchgeführt wird.
  3. Verfahren nach Anspruch 2, wobei der Katalysator mindestens ein Element, das unter Elementen der Gruppen 1 bis 16 des Langperiodensystems ausgewählt ist, oder mindestens eine Verbindung enthält, die das mindestens eine Element enthält.
  4. Verfahren nach Anspruch 3, wobei die Verbindung, die das mindestens eine Element, ausgewählt unter den Elementen der Gruppen 1 bis 16 des Langperiodensystems, enthält, ein Halogenid oder ein Oxid ist.
  5. Verfahren nach einem der Ansprüche 2 bis 4, wobei der Katalysator ein geträgerter Katalysator ist.
  6. Verfahren nach einem der Ansprüche 2 bis 5, wobei der Katalysator durch Mischen und Verdünnen mit einem weiteren Füllstoff eingesetzt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei die Reaktion in Anwesenheit von Wasser durchgeführt wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei ein Verdünnungsmittel zugegeben wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die Reaktionstemperatur 70 bis 300°C ist.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Reaktionsdruck 10 bis 1000 kPa ist.
  11. Verfahren nach einem der Ansprüche 1 bis 10, wobei das Molverhältnis von Chlor zu Allylalkohol 0,001 bis 1,5 ist.
  12. Verfahren zur Herstellung von Epichlorhydrin, welches umfaßt:
    eine erste Stufe des Umsetzens von Allylalkohol mit Chlor in einer Gasphase unter Bildung von Dichlorpropanol; und
    eine zweite Stufe des Dehydrochlorierens von Dichlorpropanol, erhalten in der ersten Stufe, unter Bildung von Epichlorhydrin.
  13. Verfahren nach Anspruch 12, wobei die Reaktion in der ersten Stufe nach einem der Ansprüche 2 bis 11 durchgeführt wird.
EP00112079A 1999-06-08 2000-06-05 Verfahren zur Herstellung von Epichlorohydrin und Zwischenprodukt davon Expired - Lifetime EP1059278B1 (de)

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JP2000131145A JP4385487B2 (ja) 1999-06-08 2000-04-28 ジクロロプロパノールの製造方法
JP2000131145 2000-04-28
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US7893193B2 (en) 2005-05-20 2011-02-22 Solvay (Société Anonyme) Method for making a chlorohydrin
US7939696B2 (en) 2005-11-08 2011-05-10 Solvay Societe Anonyme Process for the manufacture of dichloropropanol by chlorination of glycerol
US8067645B2 (en) 2005-05-20 2011-11-29 Solvay (Societe Anonyme) Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts
US8415509B2 (en) 2003-11-20 2013-04-09 Solvay (Societe Anonyme) Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel

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FR2846964B1 (fr) * 2002-11-12 2006-07-21 Procede de fabrication de 1,2-epoxy-3-chloropropane
WO2005116004A1 (en) * 2004-05-21 2005-12-08 Dow Global Technologies Inc. Process for preparing epichlorohydrin from ethane
CN100348319C (zh) * 2005-10-31 2007-11-14 东南大学 气固相合成2－氯－5－三氯甲基吡啶用的催化剂及其制备方法
EP2043984A1 (de) 2006-06-14 2009-04-08 Solvay S.A. Rohes produkt auf glyzerinbasis, verfahren zu dessen aufreinigung und dessen verwendung bei der herstellung von dichlorpropanol
US20100032617A1 (en) * 2007-02-20 2010-02-11 Solvay (Societe Anonyme) Process for manufacturing epichlorohydrin
FR2912743B1 (fr) * 2007-02-20 2009-04-24 Solvay Procede de fabrication d'epichlorhydrine
FR2913421B1 (fr) 2007-03-07 2009-05-15 Solvay Procede de fabrication de dichloropropanol.
FR2913684B1 (fr) 2007-03-14 2012-09-14 Solvay Procede de fabrication de dichloropropanol
TW200911740A (en) 2007-06-01 2009-03-16 Solvay Process for manufacturing a chlorohydrin
FR2917411B1 (fr) * 2007-06-12 2012-08-03 Solvay Epichlorhydrine, procede de fabrication et utilisation
FR2917400B1 (fr) * 2007-06-12 2009-09-18 Solvay Composition aqueuse contenant un sel, procede de fabrication et utilisation
TW200911693A (en) 2007-06-12 2009-03-16 Solvay Aqueous composition containing a salt, manufacturing process and use
TW200911773A (en) * 2007-06-12 2009-03-16 Solvay Epichlorohydrin, manufacturing process and use
EP2207617A1 (de) 2007-10-02 2010-07-21 SOLVAY (Société Anonyme) Verwendung von siliciumhaltigen zusammensetzungen zur verbesserung der korrosionsbeständigkeit von behältern
FR2925045B1 (fr) 2007-12-17 2012-02-24 Solvay Produit a base de glycerol, procede pour son obtention et son utilisation dans la fabrication de dichloropropanol
TWI478875B (zh) 2008-01-31 2015-04-01 Solvay 使水性組成物中之有機物質降解之方法
US8507643B2 (en) 2008-04-03 2013-08-13 Solvay S.A. Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol
TWI461415B (zh) * 2008-08-01 2014-11-21 Dow Global Technologies Llc 製造環氧化物的方法
TWI368616B (en) * 2008-08-01 2012-07-21 Dow Global Technologies Llc Process for producing epoxides
FR2935968B1 (fr) 2008-09-12 2010-09-10 Solvay Procede pour la purification de chlorure d'hydrogene
BRPI1006187A2 (pt) 2009-03-20 2016-03-01 Akzo Nobel Nv processo da halogenação catalítica de compostos orgânicos
WO2011092270A2 (en) 2010-02-01 2011-08-04 Akzo Nobel Chemicals International B.V. Process for preparing epichlorohydrin from dichlorohydrin
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JPS59128341A (ja) * 1983-01-10 1984-07-24 Showa Denko Kk ２，３−ジクロル−１−プロパノ−ルの製造方法
JPS59128340A (ja) * 1983-01-10 1984-07-24 Showa Denko Kk ２，３−ジクロル−１−プロパノ−ルの製造法
JPH0725712B2 (ja) * 1990-08-30 1995-03-22 昭和電工株式会社 ２，３―ジクロル―１―プロパノールの製造方法
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US8389777B2 (en) 2005-05-20 2013-03-05 Solvay (Société Anonyme) Continuous method for making chlorhydrines
US7906691B2 (en) 2005-05-20 2011-03-15 Solvay (Societe Anonyme) Method for making chlorohydrin in corrosion-resistant equipment
US8067645B2 (en) 2005-05-20 2011-11-29 Solvay (Societe Anonyme) Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts
US8106245B2 (en) 2005-05-20 2012-01-31 Solvay (Société Anonyme) Method for preparing chlorohydrin by converting polyhydroxylated aliphatic hydrocarbons
US8173823B2 (en) 2005-05-20 2012-05-08 Solvay (Société Anonyme) Method for making an epoxide
US8344185B2 (en) 2005-05-20 2013-01-01 SOLVAY (Société Anonyme Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent
US7893193B2 (en) 2005-05-20 2011-02-22 Solvay (Société Anonyme) Method for making a chlorohydrin
US7906692B2 (en) 2005-05-20 2011-03-15 Solvay (Societe Anonyme) Method for making a chlorohydrin by chlorinating a polyhydroxylated aliphatic hydrocarbon
US8420871B2 (en) 2005-05-20 2013-04-16 Solvay (Societe Anonyme) Process for producing an organic compound
US8519198B2 (en) 2005-05-20 2013-08-27 Solvay (Societe Anonyme) Method for making an epoxide
US8591766B2 (en) 2005-05-20 2013-11-26 Solvay (Societe Anonyme) Continuous process for preparing chlorohydrins
US7939696B2 (en) 2005-11-08 2011-05-10 Solvay Societe Anonyme Process for the manufacture of dichloropropanol by chlorination of glycerol
US8106246B2 (en) 2005-11-08 2012-01-31 Solvay (Societe Anonyme) Process for the manufacture of dichloropropanol by chlorination of glycerol

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TW548262B (en) 2003-08-21

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